Precipitation of particulate suspensions in hydrocarbon systems



United States Patent 3,437,466 PRECIPITATION 0F PARTICULATE SUSPENSIONS IN HYDROCARBON SYSTEMS Roy J. Betty, Chicago, Byron E. Marsh, Western Springs, and Frederick S. Marsh, Chicago, Ill., assignors, by mesne assignments, to Armour Industrial Chemical Company, a corporation of Delaware No Drawing. Filed Aug. 28, 1967, Ser. No. 663,496 Int. Cl. Cg 29/20; C101 1/22 US. Cl. 44-71 6 Claims ABSTRACT OF THE DISCLOSURE A method of precipitating particulate matter that reside as suspensions in hydrocarbons such as gasoline, kerosene, etc., by adding long chain p-aliphaticpropionamide to the hydrocarbon compound.

BACKGROUND Prior to this invention, a great deal of damage was caused by particulate matter suspensions, e.g., iron oxide and sludge suspensions in hydrocarbons such as gasoline, kerosene, jet fuel, petroleum distillates and the like. These particulate materials tended to block transporting lines, such as fuel lines in aircraft, fuel burners, etc., and adversely affected the proper combustion of the hydrocarbon such as in a burner or internal combustion engine. Such disruption of the operation of internal combustion engines occurred irrespective of Whether compression ignition or spark ignition were utilized. Also, the particles had a tendency to become lodged in the intake valves, injection nozzles and injection plungers of combustion engines.

Methods have been proposed, such as combining dispersing additives with the hydrocarbons, to disperse the sludge and the suspended particles. One such method is disclosed in US. Patent 2,805,925. This reference is directed to the use of difierent compounds to disperse particulate matter in hydrocarbons and recognizes that an inordinate amount of damage can occur from foreign particles in hydrocarbons, especially if the hydrocarbon is destined to be used as a fuel. Another method utilized to minimize eifects of sludge formation is the addition of compounds to inhibit sludge formation as exemplified by US. Patent 2,892,690. The aforementioned references to methods of inhibiting and dispersing particulate matter in hydrocarbons do not, however, cure the problem, but merely alleviate it to a degree. In the aforementioned methods, the particles are not removed, but formation of internal sludge is inhibited and sludge and foreign particles are instead evenly distributed throughout the hydrocarbon composition. It is understood that it would be preferable to remove the particulate suspensions such as oxide particles, sludge and the like from the hydrocarbon composition in order to prevent their interference with the proper combustion of the fuel as well as to prevent clogging of transport lines.

SUMMARY OF THE INVENTION Briefly described, this invention is directed to a method of precipitating suspended particles such as oxide particles and sludge in hydrocarbons by adding to the hydrocarbon compound at least one part per million of a Si-aliphaticaminopropionamide. The fi-aliphaticaminopropionamides that are utilized in accordance with this invention are prepared from the reaction of long chain fatty amines and diamines with acrylamide. The compounds that are 3,437,466 Patented Apr. 8, 1969 'ice utilized in hydrocarbon compounds in accordance with this invention are of the general formula 0 R-NHCH2CH2-(UJNH2 wherein R is selected from the group consisting of GH3(CH2)x H oHnhHay wherein x and y are integers having a sum from about 3 to 19 and n is an integer from 2 to 4. One especially suitable subclass has n equal 3.

The preparation of the fi-aliphaticaminopropionamides utilized in this invention occurs through the reaction of aliphatic amines with acrylamide in accordance with the following reaction:

wherein R is defined as in Formula I above. The reaction may be carried out by addition of the amine to a container and heating to about 60 to 100 C. and slowly adding about an equal molar amount of acrylamide. The mixture may then be stirred for a 15 to 60 minute period at a temperature of from about to C. and may be filtered through a pressure filter to remove any polyacrylamide. Almost quantitative yields of product are obtained by this method.

The hydrocarbon compositions in this invention are clarified through the addition of as little as less than on part per million of the ,8-aliphaticaminopropionamide. Different hydrocarbon compositions and various suspended materials may require a somewhat dilferent amount of fi-aliphaticaminopropionamide additive to effectively settle the undesirable material in a very short period of time. Thus, it has been found that from about 0.1 to 5 ppm. of additive in gasoline is especially effective in settling suspended fuel oil sludge. From about 5 to 50 ppm. is effective in settling fuel oil sludge and iron oxide in heavier hydrocarbons such as kerosene and diesel fuel. Therefore, it is seen that an effective concentration of more than about 0.1 ppm. additive is suitable to achieve very rapid settling of particulate matter in hydrocarbon compositions. Generally, from 0.1 to 100 ppm. of additive is suitable in the process of this invention. An excess of 100 ppm. may be used, but is undesirable from an economic standpoint.

In accordance with this invention, the term hydrocarbon is meant to include both aliphatic hydrocarbons such as gasoline, kerosene, jet fuel, fuel oil etc., and aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene and the like as well as the substituted aromatics such as styrene, divinyl benzene, u-methylstyrene,

etc. Additionally, mixtures of the aforementioned hydrocarbon compounds may also be included. Thus, the process of this invention may be used to clear foreign matter from a wide variety of hydrocarbon cleaning compositions and the like.

This invention is further illustrated by the following specific examples.

Example I B-(C -C sec-alkylamino) propionamide was prepared in the following manner. A 100 ml. round bottom flask equipped with a thermometer and magnetic stirrer was charged with 57.9 g. (0.3 mole) of C C sec-alkylamine. The temperature was raised to 90 C. and 23.4 g. (0.33 mole) of acrylamide was added portionwise over a 15 minute period. The mixture was stirred at 8595 C. for one hour, then filtered through a pressure filter to remove any polyacrylamide. The crude product was obtained as a yellow oil, 77.0 g. (95.5% yield) and had the following analysis: Neutralization equivalent, 267 (calcd 264); primary amine, 14.9%; secondary amine, 78.0%.

Example II 3-[3-(C C sec-alkylamino) propylamino] propionamide was prepared in the following manner. A 100 ml. round bottom flask equipped with a thermometer and magnetic stirrer, was charged with 44.4 g. (0.2 mole) of N-(C C sec-alkyl)-1,3-propanediamine. The temperature was raised to 80 C. and 14.2 g. (0.2 mole) of acrylamide was added portionwise over a 1530 minute period. The mixture was stirred at 80-90 C. for 30 minutes and the product obtained in almost quantative yield and had the following analysis: Neutralization equivalent, 145 (calcd 146); primary amine, 7.0%; secondary amine, 92%.

Example III Beta-aliphaticaminopropionamide additives were used to settle fuel oil sludge from kerosene. Concentrations of additives as set forth in Table I in a 1% kerosene stock solution were added to 100 mls. of kerosene in a bottle. Then gms. of fuel oil sludge and mls. of tap water were added to the bottles which were then shaken vigorously. The bottles were then allowed to stand without any movement and the time for the sludge to settle out was observed and recorded. A control was run under the same conditions with no additive. The results are shown in Table I.

Example IV The procedure of Example III was followed except 5 grns. of iron oxide particles were added instead of the fuel oil sludge. The results are shown in Table II.

TABLE II Time for Chemical additive p.p.m. particles to settle out, min.

Control, no additive (1) B-(C sec-alkylamino) propionamide. 10 25 15 50 15 100 15 B-(Cn-n sec-alkylamino) propionamide 10 35 25 35 50 35 p 100 35 B-(Cirsoc-alkylammo) propionamide. 10 5 25 5 50 5 100 5 3-[3'-(C7-q sec-alkylamino) propylamino] 10 propionamide. 20 20 20 3-[3-(C11-14 sec-alkylamino) propylamino] 10 15 propionamide. 25 15 50 15 100 15 B-Coeoamino propionamide 1g 5 2 5 50 10 100 2 4 3-[3'-(c0c0amiu0) propylamlno] propion- 10 35 amide. 25 10 50 10 100 20 l indefinitely. 2 Hours.

Example V The procedure of Example Ill was followed except that 5 gms. of fuel oil sludge was added to gasoline instead of kerosene. The results are shown in Table III.

While in the foregoing specification this invention has been described in relation to certain preferred embodiments thereof, and many details have been set forth for purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein can be varied considerably without departing from the basic principles of the invention.

We claim:

1. A hydrocarbon composition consisting essentially of a hydrocarbon compound selected from the group consisting of liquid hydrocarbon fuels and aromatic hydrocarbons and an effective quantity of a p-aliphaticamino-propionamide having the formula wherein R is an aliphatic radical selected from the group consisting of normal alkyl, normal alkenyl, secondary alkyl, normal alkyl-NH(CH normal alkenyl- NH(CH and secondary alkyl-NH(CH wherein said alkyl and alkenyl radicals have from about 6 to 22 carbon atoms and n is an integer from 2 to 4; said B-aliphaticaminopropionamide being effective to precipitate suspended particles in the hydrocarbon composition.

2. The hydrocarbon composition of claim 1 wherein said [3-aliphaticaminopropinonamide is present in a concentration of more than 0.1 ppm.

3. The hydrocarbon composition of claim 2 wherein said i8-aliphaticaminopropionamide is present in from 0.1 to 100 p.p.rn.

4. The composition of claim 1 wherein said ,B-aliphaticaminopropionamide is a B-alkylaminopropionamide having the formula R-HCH CHa -NH wherein R is selected from the group consisting of H K h):

and

a(CH2):

H NH(CH:)

CHK H2),

wherein x and y are integers having a sum from about 3 to 19 and n is an integer from 2 to 4.

5'. The composition of claim 4 wherein said hydro- References Cited UNITED STATES PATENTS 2,609,931 9/ 1952 Rodman et al. 208- XR 2,951,031 -8/ 196-0 Barclay 208180 3,282,827 11/1966 Grysiak 208180 3,305,478 2/1967 Gilson et al. 208180 DANIEL E. WYMA-N, Primary Examiner. WILLIAM J. SHINE, Assistant Examiner.

US. Cl. XJR. 252-171 

